One-Dimensional Stacking of Bifunctional Dithia- and Diselenadiazolyl Radicals: Preparation and Structural and Electronic Properties of 1,3-[(E2N2C)C6H4(CN2E2)] (E = S, Se)

M. P. Andrews, A. W. Cordes, D. C. Douglass, R. M. Fleming, S. H. Glarum, R. C. Haddon, P. Marsh, R. T. Oakley, T. T.M. Palstra, L. F. Schneemeyer, G. W. Trucks, R. Tycko, J. V. Waszczak, K. M. Young, N. M. Zimmerman, A. W. Cordes, R. T. Oakley, K. M. Young

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Abstract

The preparation and solid-state characterization of the 1,3-phenylene-bridged bis(dithiadiazolyl) and bis(diselenadiazolyl) diradicals 1,3-[(E2N2C)C6H4(CN2E2)] (E = S, Se) are reported. The isomorphous crystals of 1,3-[(E2N2C)C6H4(CN2E2)] so obtained are tetragonal, space group I41/a. Stacks of diradical molecules, linked vertically in a zigzag fashion through alternate ends by long E–––E contacts (mean 3.140/3.284 Å for E = S/Se), are arranged in pinwheellike clusters about the 41and 4¯ axes, producing complex patterns of interstack E-E contacts. Both compounds show the presence of spin defects in the lattice, and there is a very large enhancement in the paramagnetism of the sulfur compound at high temperatures. The selenium compound is a semiconductor, with a room temperature conductivity of 2 X 10-4S cm-1. Solid-state NMR experiments find enhanced relaxation times, which have their origin in the presence of a mobile paramagnetic defect. Extended Hückel band structure calculations show the materials to be semiconductors, with band gaps of about 1.0/0.8 eV for E = S/Se. Although the compounds adopt a columnar structure, the calculations indicate significant interactions between the stacks and the materials exhibit well-developed three dimensionality. The enhanced paramagnetism in the sulfur compound is attributed to the presence of thermally generated phase kinks in the lattice, whereas the selenium compound is classified as an intrinsic semiconductor.

Original languageEnglish
Pages (from-to)3559-3568
Number of pages10
JournalJournal of the American Chemical Society
Volume113
Issue number9
DOIs
StatePublished - Apr 1991

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Semiconductors
Selenium compounds
Selenium Compounds
Electronic properties
Paramagnetism
Structural properties
Sulfur Compounds
Sulfur compounds
Semiconductor materials
Defects
Temperature
Band structure
Relaxation time
Energy gap
Nuclear magnetic resonance
Crystals
Molecules
Experiments

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Andrews, M. P. ; Cordes, A. W. ; Douglass, D. C. ; Fleming, R. M. ; Glarum, S. H. ; Haddon, R. C. ; Marsh, P. ; Oakley, R. T. ; Palstra, T. T.M. ; Schneemeyer, L. F. ; Trucks, G. W. ; Tycko, R. ; Waszczak, J. V. ; Young, K. M. ; Zimmerman, N. M. ; Cordes, A. W. ; Oakley, R. T. ; Young, K. M. / One-Dimensional Stacking of Bifunctional Dithia- and Diselenadiazolyl Radicals : Preparation and Structural and Electronic Properties of 1,3-[(E2N2C)C6H4(CN2E2)] (E = S, Se). In: Journal of the American Chemical Society. 1991 ; Vol. 113, No. 9. pp. 3559-3568.
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abstract = "The preparation and solid-state characterization of the 1,3-phenylene-bridged bis(dithiadiazolyl) and bis(diselenadiazolyl) diradicals 1,3-[(E2N2C)C6H4(CN2E2)] (E = S, Se) are reported. The isomorphous crystals of 1,3-[(E2N2C)C6H4(CN2E2)] so obtained are tetragonal, space group I41/a. Stacks of diradical molecules, linked vertically in a zigzag fashion through alternate ends by long E–––E contacts (mean 3.140/3.284 {\AA} for E = S/Se), are arranged in pinwheellike clusters about the 41and 4¯ axes, producing complex patterns of interstack E-E contacts. Both compounds show the presence of spin defects in the lattice, and there is a very large enhancement in the paramagnetism of the sulfur compound at high temperatures. The selenium compound is a semiconductor, with a room temperature conductivity of 2 X 10-4S cm-1. Solid-state NMR experiments find enhanced relaxation times, which have their origin in the presence of a mobile paramagnetic defect. Extended H{\"u}ckel band structure calculations show the materials to be semiconductors, with band gaps of about 1.0/0.8 eV for E = S/Se. Although the compounds adopt a columnar structure, the calculations indicate significant interactions between the stacks and the materials exhibit well-developed three dimensionality. The enhanced paramagnetism in the sulfur compound is attributed to the presence of thermally generated phase kinks in the lattice, whereas the selenium compound is classified as an intrinsic semiconductor.",
author = "Andrews, {M. P.} and Cordes, {A. W.} and Douglass, {D. C.} and Fleming, {R. M.} and Glarum, {S. H.} and Haddon, {R. C.} and P. Marsh and Oakley, {R. T.} and Palstra, {T. T.M.} and Schneemeyer, {L. F.} and Trucks, {G. W.} and R. Tycko and Waszczak, {J. V.} and Young, {K. M.} and Zimmerman, {N. M.} and Cordes, {A. W.} and Oakley, {R. T.} and Young, {K. M.}",
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Andrews, MP, Cordes, AW, Douglass, DC, Fleming, RM, Glarum, SH, Haddon, RC, Marsh, P, Oakley, RT, Palstra, TTM, Schneemeyer, LF, Trucks, GW, Tycko, R, Waszczak, JV, Young, KM, Zimmerman, NM, Cordes, AW, Oakley, RT & Young, KM 1991, 'One-Dimensional Stacking of Bifunctional Dithia- and Diselenadiazolyl Radicals: Preparation and Structural and Electronic Properties of 1,3-[(E2N2C)C6H4(CN2E2)] (E = S, Se)', Journal of the American Chemical Society, vol. 113, no. 9, pp. 3559-3568. https://doi.org/10.1021/ja00009a051

One-Dimensional Stacking of Bifunctional Dithia- and Diselenadiazolyl Radicals : Preparation and Structural and Electronic Properties of 1,3-[(E2N2C)C6H4(CN2E2)] (E = S, Se). / Andrews, M. P.; Cordes, A. W.; Douglass, D. C.; Fleming, R. M.; Glarum, S. H.; Haddon, R. C.; Marsh, P.; Oakley, R. T.; Palstra, T. T.M.; Schneemeyer, L. F.; Trucks, G. W.; Tycko, R.; Waszczak, J. V.; Young, K. M.; Zimmerman, N. M.; Cordes, A. W.; Oakley, R. T.; Young, K. M.

In: Journal of the American Chemical Society, Vol. 113, No. 9, 04.1991, p. 3559-3568.

Research output: Contribution to journalArticle

TY - JOUR

T1 - One-Dimensional Stacking of Bifunctional Dithia- and Diselenadiazolyl Radicals

T2 - Preparation and Structural and Electronic Properties of 1,3-[(E2N2C)C6H4(CN2E2)] (E = S, Se)

AU - Andrews, M. P.

AU - Cordes, A. W.

AU - Douglass, D. C.

AU - Fleming, R. M.

AU - Glarum, S. H.

AU - Haddon, R. C.

AU - Marsh, P.

AU - Oakley, R. T.

AU - Palstra, T. T.M.

AU - Schneemeyer, L. F.

AU - Trucks, G. W.

AU - Tycko, R.

AU - Waszczak, J. V.

AU - Young, K. M.

AU - Zimmerman, N. M.

AU - Cordes, A. W.

AU - Oakley, R. T.

AU - Young, K. M.

PY - 1991/4

Y1 - 1991/4

N2 - The preparation and solid-state characterization of the 1,3-phenylene-bridged bis(dithiadiazolyl) and bis(diselenadiazolyl) diradicals 1,3-[(E2N2C)C6H4(CN2E2)] (E = S, Se) are reported. The isomorphous crystals of 1,3-[(E2N2C)C6H4(CN2E2)] so obtained are tetragonal, space group I41/a. Stacks of diradical molecules, linked vertically in a zigzag fashion through alternate ends by long E–––E contacts (mean 3.140/3.284 Å for E = S/Se), are arranged in pinwheellike clusters about the 41and 4¯ axes, producing complex patterns of interstack E-E contacts. Both compounds show the presence of spin defects in the lattice, and there is a very large enhancement in the paramagnetism of the sulfur compound at high temperatures. The selenium compound is a semiconductor, with a room temperature conductivity of 2 X 10-4S cm-1. Solid-state NMR experiments find enhanced relaxation times, which have their origin in the presence of a mobile paramagnetic defect. Extended Hückel band structure calculations show the materials to be semiconductors, with band gaps of about 1.0/0.8 eV for E = S/Se. Although the compounds adopt a columnar structure, the calculations indicate significant interactions between the stacks and the materials exhibit well-developed three dimensionality. The enhanced paramagnetism in the sulfur compound is attributed to the presence of thermally generated phase kinks in the lattice, whereas the selenium compound is classified as an intrinsic semiconductor.

AB - The preparation and solid-state characterization of the 1,3-phenylene-bridged bis(dithiadiazolyl) and bis(diselenadiazolyl) diradicals 1,3-[(E2N2C)C6H4(CN2E2)] (E = S, Se) are reported. The isomorphous crystals of 1,3-[(E2N2C)C6H4(CN2E2)] so obtained are tetragonal, space group I41/a. Stacks of diradical molecules, linked vertically in a zigzag fashion through alternate ends by long E–––E contacts (mean 3.140/3.284 Å for E = S/Se), are arranged in pinwheellike clusters about the 41and 4¯ axes, producing complex patterns of interstack E-E contacts. Both compounds show the presence of spin defects in the lattice, and there is a very large enhancement in the paramagnetism of the sulfur compound at high temperatures. The selenium compound is a semiconductor, with a room temperature conductivity of 2 X 10-4S cm-1. Solid-state NMR experiments find enhanced relaxation times, which have their origin in the presence of a mobile paramagnetic defect. Extended Hückel band structure calculations show the materials to be semiconductors, with band gaps of about 1.0/0.8 eV for E = S/Se. Although the compounds adopt a columnar structure, the calculations indicate significant interactions between the stacks and the materials exhibit well-developed three dimensionality. The enhanced paramagnetism in the sulfur compound is attributed to the presence of thermally generated phase kinks in the lattice, whereas the selenium compound is classified as an intrinsic semiconductor.

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U2 - 10.1021/ja00009a051

DO - 10.1021/ja00009a051

M3 - Article

AN - SCOPUS:0000180244

VL - 113

SP - 3559

EP - 3568

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

SN - 0002-7863

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